The present invention relates to the melding of iterative synthetic protocols with more mature research arenas for the production of utilitarian materials. Accordingly, the present invention combines the areas of dendrimers, combinatorial chemistry, and dendrimer-based electrolyte material chemistry and applies the same to the utilitarian arena of electrocomponents and enhanced electrolyte capability in solid state energy storage devices. Hence, each of these fields is addressed as the present invention provides improvements resulting from a synergy of advancements in each of these fields in combination.
By way of background, rapid advancement in the field of “dendritic chemistry” (Newkome at al., VCH: Weinheim, Germany, 1996) has afforded scientists with a new arsenal of techniques for the construction of utilitarian materials. Testament to interest in this burgeoning area is evidenced by ubiquitous literature reports on the subject since its discovery (1978) and commencing rise (mid-1980s). Central to dendritic chemistry is the “iterative synthetic methodology”, which has afforded new pathways to the construction of complex, high molecular weight molecules.
The realization of “dendrimers”, and related constructs such as “hyperbranched” polymers (Hult et al., 1999) and “dendrimer-polymer hybrids”, (Roovers et al., 1999) has thus facilitated advances in the ability to design and build architecturally homogeneous branched molecular assemblies.
There are inherent limitations imposed on these structures due primarily to 1) the repetitive application of a single building block for tier construction leading to functional group uniformity on the surface, as well as the interior, of the branched structure and 2) a lack of interchangeable monomers that would facilitate the incorporation of diverse application oriented functionality and thus allow the creation of utilitarian assemblies.
These limitations are addressed via 1) the development of a “modular” set of application-oriented branched building blocks for dendritic synthesis (Young et al., 1994) aimed directly at enhanced solid-state energy storage and release devices (e.g., lithium battery performance); 2) the use of combinatorial-based tier construction techniques (Newkome et al., Isocyanate-Based Dendritic Building Blocks: Combinatorial Tier Construction and Macromolecular Property Modification, Angew. Chem., Int. Ed. Engl., 1998) for the creation of unimolecular, multi-component assemblies whereby the individual components can act in concert to produce a desired physiocochemical effect, and 3) use of branched architectures to fabricate, template, and stabilize metal and non-metal particles, composites, and clusters.
Specifically, advancement in lithium- and lithium rocking chair-battery efficiency (Lipkowski et al., 1994; Owen, J. R., 1997) is shown to result from 1) improved electrolyte materials based on highly stable, polyethylene glycol functionalized, saturated hydrocarbon-type dendrimers, and 2) significantly reduced inter-electrode separations. Ultimately, this has led to branched assemblies possessing mutually compatible and synergistic units capable of triggered electrochemical discharge. This forms the basis of a logical evolution of iterative chemistry that melds the maturity of classical polymer, organic, and inorganic chemistries, as well as emerging fields that include “C60” technology, with the strengths of dendritic chemistry.
To date, a diverse set of branched monomers have been crafted for the introduction of 1) high-density surfaces and 2) “latent” functionality to be used, or activated, after primary dendritic construction, including: terpyridine (Newkome, et al., J. Mater. Chem. 1997; Newkome et al., Chem. Commun. 1998) arylamne hexaester, (Newkome et al., Synlett 1992) arylaminoterpyridyltriester, (Newkome et al., Chem. Commun. 1999) and arylnitroanthraquinonoid (Narayanan et al., 1999; Newkome et al., Designed Monomers and Polymers, 1999; Newkome et al., Macromolecules, 1999; Newkome et al., Macromolecules, 1997).
Additionally, applicants have recently reported the preparation of β-cyclodextrin branched building blocks has recently reported (5) for use in self-assembly studies predicated on molecular recognition and host-guest inclusion. (Newkome et al., Chem. Commun., 1998).
A novel family of isocyanate, 1→3 branched buildings blocks has been developed and reported (Newkome et al., U.S. Pat. No. 4,154,853, 1992; Newkome et al., Angew. Chem., Int. Ed. Engl., 1991; Newkome et al., Chem. Commun., 1996; Newkome et al., Tetrahedron Lett., 1997; Newkome et al., Designed Monomers and Polymers, 1997) that allows 1) rapid physiocochemical modifications of diverse macromaterials (Newkome et al., Chem. Commun., 1996) and 2) “combinatorial-based” multiple functional group incorporation. (Newkome et al., Combinatorial Chem., 1999; Newkome et al., U.S. Pat. No. 5,886,126, 1999; Newkome et al., U.S. Pat. No. 5,886,127, 1999). Each member of this series relies on an isocyanate moiety for monomer connectivity. Steric demands associated with the adjacent branch junctures give rise to unprecedented isocyanate stability. These materials are generally solids that are stable in air, which facilitates handling and storage. For example, the isocyanatotriester is a white crystalline soli (mp 60-62° C.) that reacts readily with amines and requires slightly more vigorous conditions to react with alcohols; its crystal structure has been reported. (Newkome et al., Tetrahedron Lett., 1997).
Eloquent work in the area of self-assembly by Stang (1), Lehn (2), and many others (3-7), has prompted our investigation of the potential to spontaneously construct Ru-based (macro)molecules. More specifically, our goal involved the design and preparation of polyterpyridyl ligands that would form the basis of a “modular building block set” (8) capable of being used to access “higher order” (fractal) architectures. We herein report the construction of a bis(terpyridine) monomer that facilitates the preparation of hexaruthenium macrocycles.
Linear bis(terpyridyl) monomers have been employed for the formation of layered polyelectrolyte films (9), Ru(II)-based dendrimers (10), helicating ligands (11), grids (12), racks (13), and photoactive molecular-scale wires (14), to mention but a few. Whereas, progress in directed synthesis of cyclic rigid structures can be found in “shape persistent” phenylacetylenes (15-17), diethynylbenzeme macrocycles (18), and a 24 phenylene hexagon (19), advances via self-assembly has yielded, for example, chiral (20) and achiral (21) circular helicates, cylindrical cage structures (22), Pt-coordinated bipyridyl squares (23), and metal-templated [2]catenanes (24, 25), and cyclic porphyrin trimers (26).
In view of the above, it is desirable to develop further compounds, and in the larger sense, various means for improving and enhancing electrolyte and electrocomponents in solid state, energy storage devices. It would be desirable to be able to meld together iterative processes utilized in dendritic chemistry with combinatorial processes which have also been highly developed in dendritic chemistry towards multiple unit positioning within dendritic structures and other architectures in order to obtain improvements and enhancements.